In this work, a series of Ti(iv)/ZnIn2S4 composite photocatalysts were demonstrated by a facile two-step method. A Ti(iv) component was introduced into the flower-like ZnIn2S4 microspheres, which could act as an effective hole co-catalyst, shorten the charge migration distance, provide abundant active sites, inhibit the recombination of electron-hole pairs and mitigate the photocorrosion effect of ZnIn2S4. Benefiting from these favorable properties, the amorphous Ti(iv) modified ZnIn2S4 showed excellent H2 evolution performance which can reach 3685.2 μmol g-1 h-1, higher than that of pure ZnIn2S4 (2335.5 μmo g-1 h-1). Meanwhile, the modified ZnIn2S4 exhibits good stability after several consecutive hydrogen production runs. The photocatalytic purification of methyl orange (MO) in simulated wastewater was further tested. The degradation efficiencies, TOC removal, and highest hydrogen production were respectively 95%, 28.8% and 2650 μmol g-1 h-1. These results may provide an inspiration for tailoring multifunctional semiconductors with amorphous metal ions, which can be used as a photocatalytic H2 evolution catalyst with high-efficiency, as well as purifying the wastewater simultaneously.